Emulsion



aiente Nov. 23, 1943 means ESKON Morris Katzman, Frank J. Calm, andAlbert K. Epstein, Chicago, Ill., assignors to The Emulsol Corporation,Chicago, 11., a corporation of Illinois No Drawing. Application December19, 1940.

' Serial No. 370,810

Claims.

This invention relates to the preparation of emulsions or dispersionscontaining aqueous and ole'aginous materials and compositions therefor,and is particularly concerned with the preparation of cosmeticpreparations in the form of emulsions of oleaginous and aqueousmaterials, which emulsions have an acid reaction or a pH below 7.

Emulsions or dispersions of the character referred to have heretoforebeen prepared in which emulsifying or dispersing agents, or combinationsthereof, of numerous types, have been utilized. While the stability ofthese emulsions or dispersions is enhanced by the addition of saidemulsifying or dispersing agents or combinations there- 01, still, inmany instances, the improvements have not been sufiicientiy marked so asto provide a completely satisfactory solution to the problemsconfronting those versed in the art Among the numerous emulsifying ordispersing agents whose use has been suggested for enhancing thestability of oleaginous-aqueous emulsions are the higher molecularweight aliphatic alcohol sulphates and sulphonates, the sulphonated oilssuch as Turkey-red oil, the sulphates and phosphates of the higher fattyacid monoglycerides, monoglycerldes and diglycerides of higher molecularweight aliphatic, particularly, fatty acids, and the like. It has alsobeen proposed to utilize mixtures of higher fatty acid monoglycerides orthe like with salts of sulphonic acid derivatives or sulphuric acidesters of higher molecular weight aliphatic alcohols, as, for example,combinations of monolaurin with lauryl sodium sulphate and the like. Ithas been proposed also to employ combinations of monoglycerides or otherpartially esterified polyhydric alcohols together with fatty acid aminoproducts resulting from reacting higher molecular weight fatty acid acylhalides with protein decomposition products. Furthermore, the suggestionhas been made to utilize, as emulsifying agents for aqueous-oleaginousemulsions, mixtures of agents one of which contains a colloidal cationand the other a colloidal anion. In none of these cases have the agentswhich have been proposed to be used been found fully satisfactory.

In accordance with the present invention, emulsions or dispersions ofexcellent character and stability, particularly cosmetic emulsionshaving an acid reaction, are produced by utilizing a combination ofcertain agents, hereinafter defined and described in detail. Theseagents comprise an intimate mixture of (1) cation-active substances and(2) non-ionic substances, the

non-ionic substances substantially predominating in amount over thecation-active substance at least in mostcases.

The cation-active substances may be of aliphatic, earboxylic, orheterocyclic character and, as will be understood, comprise substancesin which the surface activity is due to a group or radical present inthe cationic portion of the molecule. Among the cation-active'compoundswhich may be employed in accordance with the present invention are thebases or their salts, such as may be derived from pentavalent nitrogen,and further the sulphonium, phosphonium and arsonium, etc. bases andtheir salts. The quaternary ammonium compounds are examples ofsatisfactory compounds, the pyridonium or pyridinium compounds beingspecific examples thereof. In the bases or their salts, the innocuousanions may be hydroxide, chloride, sulphate,

bromide, iodide, acetate, etc. The groups inducing cation activitycomprise long chain groupings such as aliphatic hydrocarbon chainshaving at least six and preferably from twelve to eighteen carbon atoms.The long chain groupings may be composed of two or more benzene nucleior.

other cyclic radicals, either combined directly or, for example, throughcarbon or nitrogen or tertiary amines.

other linkages, with or without aliphatic chains substituted for thehydrogen in rings.

Examples of cation-active substances which may be used in accordancewith our invention include octyl pyridinium iodide, dodecyl pyridiniumbromide, hexadecyl pyridinium iodide, octadecyl pyridinium bromide,dodecyl pyridinium iodide, dodecyl pyridinium chloride, dodecyl-triethylammonium iodide, octyl-triethyl ammonium .iodide, decyl-triethylammonium iodide, dodecylacids, particularly, fatty acids. examples ofsuch esters are, for example, higher 'mono-olein, monq palmitin;

This group of substances is disclosed in the copending application ofAlbert K. Epstein and Morris Katzman, Serial No. 370,354 filed December16, 1940.

The non-ionic substances are, in general, allphatic polyhydroxysubstances or polyhydric al- ,boxylic, aliphatic (including coholsincompletely esterifled with higher molecular weight aliphatic(including cycloaliphatic) Representative molecular weight fatty acidmonoglycerides such as monocaprylin, monolaurin,

higher molecular weight fatty acid mono-esters oi polyglycerols, glycolsand polyglycols such as the stearic acid mono-ester of diglycerol, theoleic acid monoester of ethylene glycol, the-oleic mono-ester oidiethylene glycol, and the like.

Among the aliphatic polyhydroxy substances whose partial esters comprisethe vnc nionic agents which are used in combination with theaforementioned cation-active substances, are, for

example, including some previously mentioned,

glycerol; glycols such as ethylene glycol, propylene glycol,trimethylene glycol, butylene glycol and the like; polygly'cols such asdiethylene glycol;

- pehtaerythritok' quercitol; dihydroxy acetone;

polyglycerols such as diglycerol, triglycerol, tetraglycerol and thelike including mixtures thereof;

"carbohydrates or sugars including mono', diand monostearin,

polysaccharides such as dextrose, sucrose, xylose,

arabinose, galactose, fructose, maltose, mannose, dextrin, starch, andthe like; sugar alcohols such as arabitol, mannitol, sorbitol anddulcitol; and

'polyhydroxy carboxylic acids such as tartaric acid, mucic acid,saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannonicacid, trihydroxyglutaric acid, glyceric acid, carboxylic oxidationproducts 01 polyglycerols, others of similar character, and hydroxyethyland hydroxypropyl ether derivatives of the above, as, for example:

' CH1O-CHt-CH:OH

CHQ- CHr-CH|OH CHr-O-CHr-CHsOH cHEo-cm-omon HOCHr-CH20H H-O-CHr-CHaOHHr-O-CHr-CHaOH CHr-O-CHr-CHgOH n-o-cnr-onion n-o-onkcmon ore-o-cm-cmonH-d-cm-QmQB nr-o-cm-cmon 7 stances 'to form the non-ionic agents whichare used in accordance with the present invention may be selected from alarge group including, among those mentioned, straight chain andbranched chain, saturated and unsaturated, car- I cycloaliphatic) fatty,such as caprylic acid, caproic acid, capric acid, pimelic acid, sebacicacid, behenic acid, arachidic acid, cerotic acid, erucic acid, melissicacid, stearic acid, oleic acid, ricinoleic acid, ricinelaidlc acid,ricinostearolic acid, linoleic acid, linolenic acid, lauric acid,myristic acid, palmitic acid, mixtures of any two or more of the abovementioned acids or other acids, mixed higher fatty acids derived fromanimal or vegetable sources, for example, lard, coconut oil, rapeseedoil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil,cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castoroil, seal oils, whale oil, shark oil and other fish oils, partially orcompletely hydrogenated animal and vegetable oils such as thosementioned; oxidized and/or polymerized higher fatty acids or higherfatty acids derived from oxidized and/or polymerized triglyceride oils;acyloxy carboxylic acids such as hydrox and alpha-hydroxy highercarboxylic, aliphatic and fatty acids such as i-hydroxy stearic acid,dlhydroxypalmitic acid, dihydroxystearic acid, dihydroxybehenic acid,alpha-hydroxy capric acid, alpha-hydroxy stearic acid, alpha-hydroxypalmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid,alpha-hydroxy cocount 011 mixed fatty acids, alpha-hydroxy margaricacid, alpha-hydroxy arachidic acid, and the ployed in accordance withthe present invention.

It will be appreciated that the proportions thereof may be varied, thatvarious mixtures 01' diiierent-agents or'substances of the two types maybe employed and that other modifications and variations may be madewithout departing from the guiding principles which are disclosedherein:

Example 1 250 grams of monostearin and 50 grams of a product having theformula C|IH$QC-OCIHI7NH CHI-? NHI were mixed together at 100 degrees C.until a clear liquid was obtained and the mass was then permitted tocool.

Example 2 grams of monostearin were heated to degrees C. and were mixedwith 10 grams of lauryl pyridinium iodide. At 80 degrees C., the productwas a clear yellow liquid.

Example 3 45 grams of the stearic acid mono-ester of diethylene glycoland grams of a compound having the following formula were heatedtogether at approximately 100 degrees C. until a clear solution wasobtained. The mass was then allowed to 0001.

Example 4 90 grams of monostearin were heated to 125 degrees C. andmixed with grams of a compound having the following formula:

until a clear solution was obtained. The mass was then permitted tocool.

Exampl 5 80 grams of monostearin were heated to 120 degrees C. and mixedwith grams of the hydrochloride of the lauric acid ester ofmonoethanolamine until a clear solution was obtained, whereupon themixture was permitted to cool.

Example 6 90 grams of monostearin were heated to 125 degrees C. andmixed with 10 grams of cetyl pyridinium iodide until a clear solutionwas obtained. The mass was then permitted to cool.

.The oleaginous-aqueous emulsions or dispersions in which thecombination of cation-active substances and non-ionic agent areincorporated may be, in general, of varying character, but especiallysatisfactory results have been obtained in connection with acid-reactingemulsions, particularly cosmetic emulsions oi'this type. A noteworthyexample of the type of cosmetic emulsion'to which the present inventionrelates are cosmetic astringent creams. In general, such creams contain,in addition to oleaginous and aqueous constituents, a salt of a strongacid with a polyvalent metal, such as aluminum chloride and aluminumsulphate. Although, as stated, the invention is especially concernedwith cosmetic emulsionsof the character indicated, it will beappreciated that the invention is not so limited. Emulsions ordispersions containing oleaginous materials and aqueous materials, andparticularly those having an acid reaction, to which the principles ofthe present invention may be adapted include also medicinal andpharmaceutical emulsions, furniture polishes, automobile polishes,certain resin emulsions, and the like.

The following examples are representative of types of emulsions whichmay be made in accordance with the principles of the present invention:

Example A Example B (1) 42 grams of a mixture of monostearin andmonoethanolamine (said mixture containing 90% of monostearin and 10% ofthe hydrochloride of the lauric acid ester of monoethanoiatccine),

14 grams of spermaceti, 4 grams of glycerine, and

cc. of water were mixed together and brought to a boil, with stirring,until a uniform emulsion or dispersion was obtained. The emulsion wasthen permitted to cool to about 50 degrees C.

(2) A solution was made by heating a mixture, to about'60 degrees 0., of20 grams or" .AlClafiHzO, 20 grams of A12(SO4)3.18H2O, and. .0 cc. ofwater. It was allowed to cool to about 50 degrees C;

(3) The solution produced in part 2 hereof was then added slowly andwith constant stirring to the emulsion of" part 2 hereof. A medium viecous white emulsion resulted which, on standing several hours, set to afirm cream having excellent smoothness and texture. The cream was highlysatisfactory as an anti-perspirant.

Example (2' was stirred constantly during the addition and until themass had reached room temperature. The product comprised a finedispersion of war: which could be diluted with water. The resultingproduct was very satisfactory for the coating and impregnating of paperstock.

Example D 20 grams of a mixture of the stearic acid mono ester ofdiethyleneglycol and a compound havingthe following formula (the stearicacid mono-ester of diethyieneglycol the hydrochloride of the lauric acidester of comprising 90% of said mixture), were melted and mixed with 30grams of light mineral oil, the mixture being heated to degrees C. Saidmixture was then added slowly and with constant stirring to a solutioncontaining d5 cc. of water and 5 grams of glacial acetic acid, saidsolution also being maintained at about 80 degrees C. The mixture wasconstantly stirred until room temperature was reached. The product was awhite, viscous emulsion at room temperature and was useful as afurniture polish.

Example E 10 grams of the product of Example -3, id grams of lightmineral oil and 5 grams 0;? sper= maceti were heated together to 80degrees C. whereupon a clear oleaginous solution was formed. The samewas then added slowly and with constant stirring to a solutioncontaining 40 cc. of water and 5 grams of tartaric acid, said solutionalso being at 80 degrees C. The mass was constantly stirred during theaddition and the stirring was continued until the resulting emulsionreached room temperature. The prod= uct, which was a heavy, whiteemulsion, was very useful as a cosmetic cream.

7 Example F CH: I (mm-o-o-t-Na. c1

(2) 20 grams of the mixture of part 1 hereof, 20 grams of cottonseedoil, 8 grams oi. spermaceti, 4. grams of paraflin wax, and 9 grams ofmineral oil were heated together to 80 degrees C. whereuponla clear oilysolution was formed. Said solution was then added slowly and withconstant stirring to a solution containing 40 cc. of water and 1 gram oftartaric acid, also maintained at a temperature of 80 degrees C. Thestirring was continued until the final emulsion product reached roomtemperature. The emulsion was of smooth, excellent consistency and wasparticularly useful for cosmetic purposes.

The proportions of the cation-active substance and non-ionic agentemployed in the emulsions or dispersions are subject to relatively wide,variations, the amount utilized being dependent, among other things,upon the potency of the sub stances or agents selected, the specificcharacter of the emulsions with which they are utilized, and

the exact results desired. In general, from about 0.1% to 5.0%, basedupon the weight of the oleas stearic acid, palmitic acid, and the like:lanolin or wool grease, and numerous other materials of the characterindicated. 7

What we claim as new and desire to protect by Letters Patent 01' theUnited States'is:

1. An emulsion, having a normally acid reaction, containing oleaginousmaterial, aqueous material, and small proportions of (1) an allphaticpolyhydroxy substance incompletely esterified with a higher molecularweight fatty acid, and (2) a cation-active substance in'the form of ahydrochloride of a higher molecular weight fatty acid ester of ahydroxy-alkyl primary amine.

2. An emulsion containing an oleaginous mat of a mineral acid salt of ahigher molecular aginous constituent or constituents, is effective formost purposes but the amount may be increased substantially, V

It will be understood that the term oleaginous, as used in the claims,is intended to include water-repellent or hydrophobic substances such asoils and fats of animal, vegetable and mineral origin, waxes such asparaffin, carnauba wax, beeswax, montanwax, candellila wax, and

the like; higher molecular weight fatty. acids such weight fattyacid'ester of an hydroxy non-tertiary amine, and an aliphaticpolyhydroxy substance incompletely esterified with a higher molecularweight fatty acid.

5. An acid-emulsifying agent comprising a 7 mixture of a cation-activesubstance, in the form of a hydrochloride of higher molecular weightfatty acid esters of monoethanolamine, with monostearin, the monostearinbeing substantially in excess of the cation-active substance.

MORRIS KATZMAN. FRANK J. CAHN. ALBERT K. EPSTEIN.

